The production of organic compounds using synthesis gas, which is a mixture of carbon monoxide and hydrogen, or from carbon monoxide as one of the reactants has been known for a significant period of time. It is well known that one can produce methanol directly from synthesis gas and that methanol can be further reacted by hydroformylation, homologation and carbonylation reactions to produce acetaldehyde, ethanol and acetic acid or its methyl ester, respectively. It is also known that alcohols, esters, ethers, and other organic compounds can be reacted with synthesis gas or carbon monoxide to produce oxygenated organic compounds. The difficulties, however, have resided in the ability to carry out any one of these chosen reactions to produce the desired compound at acceptable efficiency, conversion rate and selectivity.
In almost all instances the reaction is generally catalyzed using a Group VIII transition metal compound as the catalyst and a halogen as the promoter. It is known that many other metal compounds and promoters can be used. In addition, the prior art has disclosed the use of secondary activators or ligands in conjunction with the metal catalysts and promoters. These secondary activators can be other metallic salts or compounds, amines, phosphorus compounds, as well as a multitude of other compounds that have been disclosed in the published literature. Thus, a typical catalyst system contains the metal atom catalyst, promoter and, optionally, ligands, solvents and secondary activators. Though a significant amount of literature does exist describing the production of carboxylic acids it is believed that it does not disclose or suggest the present invention. Several of the pertinent patents in this area are discussed below.
French Pat. No. 2,317,269, filed by Compagnie Des Metaux Precieux and published on Feb. 4, 1977, discloses the production of aliphatic carboxylic acids by the reaction of an alcohol with carbon monoxide in the presence of a catalyst containing at least three essential components, iridium atom, copper atom and halogen. This is not our process.
In European Patent Application No. 0018927; filed by Gauthier-Lafaye et al on Apr. 23, 1980 and published on Nov. 12, 1980, there is described a process for the production of monocarboxylic acids by the carbonylation of an alcohol using a nickel catalyst, a halide and a solvent. In this reference synthesis gas is used. In the instant process an organic acid is produced from an organic formate ester in the presence of carbon monoxide and a rhodium complex as the catalyst. No carbonylation is required in the instant process.
U.S. Pat. No. 3,060,233, issued to Hohenschutz on Oct. 23, 1962, discloses the carbonylation of methanol to acetic acid using a metal of the iron group of the Periodic Table and a halide. It does not disclose use of the instant rhodium complex at the mild pressure and temperature conditions employed herein.
U.S. Pat. No. 3,769,329, issued Oct. 30, 1973 to Paulik et al, discloses the use of a conventional rhodium catalyst and conventional ligands. The preferred mode of operation of this prior art process requires a large excess of water to ensure selectivity to acetic acid. This reference employs relatively extreme reaction conditions of temperature and pressure, and makes no distinction relating to the suitability of useful ligands. In addition, carbon monoxide is consumed which indicates a different kind of reaction than that of the instant invention.
U.S. Pat. No. 4,212,989, issued to Isshiki et al., on Jul. 15, 1980, describes a process for producing carboxylic acids or their esters by reacting an alcohol or an ether with carbon monoxide using a Group VIII metal catalyst and an iodine promoter. The reference contains no disclosure or suggestion of the production of carboxylic acids employing a specific rhodium complex under mild reaction conditions.
Another known procedure for producing acetic acid is the catalytic isomerization of methyl formate as shown by the reaction: EQU CH.sub.3 OOCH.fwdarw.CH.sub.3 COOH
This procedure is shown in U.S. Pat. No. 1,697,109, issued to Henry Dreyfus on Jan. 1, 1929. The process described is a vapor phase isomerization reaction carried out at 200.degree. C. to 450.degree. C. at a pressure, for example, on the order of 200 atmospheres using a metal oxide or acetate catalyst. That is typical of the extreme reaction conditions normally used in this area of technology.
U.S. Pat. No. 2,508,513, assigned to Celanese Corporation and issued on May 23, 1950 claims a Group VIII metal atom based catalyst, e.g. nickel promoted with methyl iodide for the isomerization of methyl formate to acetic acid, carried out at 300.degree. C. to 400.degree. C. and at a pressure up to 6000 psig. Carbon monoxide may be present. It does not disclose the use of the rhodium complex catalyst of the present invention at low reaction temperature and pressure.
U.S. Pat. No. 3,798,267, issued Mar. 19, 1974, relates to the conversion of methyl formate to acetic acid in the presence of a catalyst system consisting essentially of activated carbon and a halogen promoter. The reference uses catalyst and starting materials different than those employed in the invention of this application.
U.S. Pat. No. 4,194,056, filed by Antoniades and issued Mar. 18, 1980, discloses the production of carboxylic acid from methyl formate using a soluble rhodium catalyst, halogen promoter and carbon monoxide. This is not the process of the instant invention, nor does this reference disclose or suggest the use of a specific rhodium complex nor the instant mild reaction conditions nor the instant LiI:CH.sub.3 I halogen source and the unexpected results achieved by their use.
British Patent Specification No. 1,286,224, issued Aug. 23, 1972 to Wakamatsu et al., relates to the reaction of methyl formate with carbon monoxide in contact with a rhodium catalyst and a halogen promoter to produce acetic acid. It contains no recognition of the distinct advantages achieved with the use of the instant specific rhodium complex nor of the instant mild reaction conditions.
British Patent Specification No. 1,293,193, issued Oct. 18, 1972 to Japan Gas-Chemical Company, Inc., relates to the direct conversion of formic acid esters to their corresponding carboxylic acids, in the presence of carbon monoxide, a catalyst that is a Group IIb or VIII metal and an organic polar solvent. It does not disclose use of the specific rhodium complexes of this invention nor of the mild operating conditions of the present process.
Japanese Patent Publication 50-16773, filed by Kuraishi et al and published on Jun. 16, 1975, discloses the production of an organic acid from the corresponding formic acid ester in the presence of carbon monoxide using a catalyst system containing cobalt, iron or mercury and a halogen plus an alkali metal salt of a lower aliphatic carboxylic acid, triamine or cyclic amine. The process is said to be carried out at high operating pressures.
Japanese Patent Publication No. 51-65703, filed by Mitsui Petrochemical and published on Jun. 7, 1976, discloses the reaction of methyl formate in the presence of carbon monoxide using a system containing a rhenium catalyst and halogen compound to produce some acetic acid. The principal product is methyl acetate. Acetic acid rates and selectivities are low.
Japanese Patent Publication No. 56-22745, filed by Wada et al., and published Mar. 3, 1981, discloses the isomerization of a formic acid ester to the corresponding acid in the presence of carbon monoxide, palladium atom, halogen and base. Acetic acid selectivity is low.
Japanese Patent Application No. 56-73040, filed by Isshiki et al., and published on Jun. 17, 1981, relates to a process for producing acetic acid by isomerizing methyl formate in the presence of carbon monoxide using a nickel catalyst, an iodine compound and an organic nitrogen compound.
Japanese Patent Application No. 56-83439, filed by Isshiki et al., and published Jul. 8, 1981, discloses a method for producing acetic acid by heating at elevated temperatures and pressures methyl formate and carbon monoxide in contact with a catalyst containing palladium, ruthenium and/or iridium metal atom and a halide promoter.
None of the previous five Japanese Patent Applications disclose a process for producing a carboxylic acid from an organic formate ester using a catalyst mixture which includes a rhodium complex, lithium iodide and methyl iodide.
European Patent Application No. 0045637, published Feb. 10, 1982 discloses converting formic acid esters to their corresponding carboxylic acids using a soluble iridium salt catalyst and an iodine promoter in the absence of an initial CO-pressure.
It can also be seen that the prior art contains many disclosures dealing with the catalytic production of acetic acid, including its production by isomerizing methyl formate. The art also discloses the production of other organic carboxylic acids from isomerization of other formate esters. One of the disadvantages of many of these reference processes is the presence of water with the eventual need to remove it from the desired product. This removal is both complicated and costly. Other disadvantages often include the simultaneous occurrence of other reactions leading to the formation of by-products, such as dimethyl acetal, ethanol, etc. These reactions compete with the organic acid production resulting in low conversion rate and selectivity to the desired organic acid-product.
Frequently, as shown above, typical prior art processes employing rhodium catalyst require rather harsh reaction conditions of temperature and pressure to obtain satisfactory yields of products. Such reaction conditions require use of expensive reactors, engender excessive energy costs, often lead to undesired by-products and cause excessive corrosion problems.
Many processes employed for producing organic acids use a catalyst system containing a source of metal atom and a source of halide atom. However, none of the references recognize the advantages of employing lithium iodide alone or admixed with methyl iodide in conjunction with a rhodium complex catalyst for efficient low temperature and pressure operations.